Organoleptic compounds and their use in perfume compositions

ABSTRACT

The present invention is directed to compounds which possess unique organoleptic propertied of the general formula 
                         
wherein R is a hydrogen or selected from the group consisting of C 1 -C 7  moieties and the use of these materials as a fragrance chemical to enhance fragrance in perfumes, toilet waters, colognes, personal products and the like.

STATUS OF RELATED APPLICATIONS

This application is a continuation-in-part of U.S. Ser. No. 11/298,117,filed on Dec. 9, 2005, the contents hereby incorporated by reference asif set forth in its entirety.

FIELD OF THE INVENTION

The present invention relates to new chemical entities and theincorporation and use of the new chemical entities as fragrancematerials.

BACKGROUND OF THE INVENTION

There is an ongoing need in the fragrance industry to provide newchemicals to give perfumers and other persons the ability to create newfragrances for perfumes, colognes and personal care products. Those withskill in the art appreciate how differences in the chemical structure ofthe molecule can result in significant differences in the odor, notesand characteristics of a molecule. These variations and the ongoing needto discover and use the new chemicals in the development of newfragrances allows perfumers to apply the new compounds in creating newfragrances.

SUMMARY OF THE INVENTION

The present invention provides novel chemicals, and the use of thechemicals to enhance the fragrance of perfumes, toilet waters, colognes,personal products and the like. In addition, the present invention isdirected to the use of the novel chemicals to enhance fragrance inperfumes, toilet waters, colognes, personal products and the like.

More specifically, the present invention is directed to the novelcompounds, represented by Formulas I-III set forth below:

wherein R and R′ each independently is selected from the groupconsisting of hydrogen and C₁-C₇ moieties, and the use of thesecompounds as a fragrance chemical to enhance fragrance in perfumes,toilet waters, colognes, personal products and the like.

Another embodiment of the invention is a method for enhancing a perfumecomposition by incorporating an olfactory acceptable amount of thecompounds provided above.

These and other embodiments of the present invention will be apparent byreading the following specification.

DETAILED DESCRIPTION OF THE INVENTION

In Formulas I, II and III above, wherein R and R′ each independently isselected from the group consisting of hydrogen and C₁-C₇ moieties, andthe use of these compounds as a fragrance chemical to enhance fragrancein perfumes, toilet waters, colognes, personal products and the like.Representative moieties include alkyl groups such as but not limited to:CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, CH(CH₃)CH₂CH₂CH₃, CH₂CH(CH₃)CH₂CH₃ andCH₂CH₂CH(CH₃)CH₃, cyclopropyl, cyclobutyl, cyclopentyl; as well asunsaturated moieties including but not limited to:

CH═CHCH₂CH₂CH₃, CH₂CH═CHCH₂CH₃, CH₂CH₂CH═CHCH₃, and CH═C(CH₃)CH₂CH₃.Those with skill in the art will appreciate that the present inventionincludes various isomers including chiral or optically active isomers,which are contemplated within the scope of the present invention.

In the preferred embodiment of the invention, the novel compounds of thepresent invention are represented by the following structures:

Those with the skill in the art will appreciate that the compound ofStructure I is Cyclopropanepentanol, Alpha, Alpha, Epsilon-Trimethyl-,the compound of Structure II is Cyclopropane,1-(1,5-Dimethyl-4-Hexenyl)-1-(methoxymethyl)-, the compound of StructureIII is Cyclopropanepropanol, alpha, 2-Diethyl-Alpha, 2-Dimethyl.

Structure I is described as having fresh strong, citrus, lime and herbalfragrance notes. Structure II has strong, citrus, rosy and floralfragrance notes. Structure III has refreshingly light, clean, floral,citrus, lemon, orange and sweet fragrance notes.

The compounds of the present invention may be prepared from thecorresponding compounds by the following sequences using Yamamoto andSimmon-Smith cyclopropanation reactions.

Those with skill in the art will recognize that some of the compounds ofthe present invention have a number of chiral centers, thereby providingnumerous isomers of the claimed compounds. It is intended herein thatthe compounds described herein include isomeric mixtures of suchcompounds, as well as those isomers that may be separated usingtechniques known to those having skill in the art. Suitable techniquesinclude chromatography such as HPLC, and particularly gel chromatographyand solid phase microextraction (“SPME”).

We have discovered that the fragrance compounds of Formulas I-III arewell suited for use as a fragrance ingredient.

The use of the compounds of the present invention is widely applicablein current perfumery products, including the preparation of perfumes andcolognes, the perfuming of personal care products such as soaps, showergels, and hair care products as well as air fresheners and cosmeticpreparations. The present invention can also be used to perfume cleaningagents, such as, but not limited to detergents, dishwashing materials,scrubbing compositions, window cleaners and the like.

In these preparations, the compounds of the present invention can beused alone or in combination with other perfuming compositions,solvents, adjuvants and the like. The nature and variety of the otheringredients that can also be employed are known to those with skill inthe art.

Many types of fragrances can be employed in the present invention, theonly limitation being the compatibility with the other components beingemployed. Suitable fragrances include but are not limited to fruits suchas almond, apple, cherry, grape, pear, pineapple, orange, strawberry,raspberry; musk, flower scents such as lavender-like, rose-like,iris-like, carnation-like. Other pleasant scents include herbal andwoodland scents derived from pine, spruce and other forest smells.Fragrances may also be derived from various oils, such as essentialoils, or from plant materials such as peppermint, spearmint and thelike.

A list of suitable fragrances is provided in U.S. Pat. No. 4,534,891,the contents of which are incorporated by reference as if set forth inits entirety. Another source of suitable fragrances is found inPerfumes, Cosmetics and Soaps, Second Edition, edited by W. A. Poucher,1959. Among the fragrances provided in this treatise are acacia, cassie,chypre, cyclamen, fern, gardenia, hawthorn, heliotrope, honeysuckle,hyacinth, jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly-cuthay, orange blossom, orchid, reseda, sweet pea, trefle, tuberose,vanilla, violet, wallflower, and the like.

Olfactory effective amount is understood to mean the amount of compoundin perfume compositions the individual component will contribute to itsparticular olfactory characteristics, but the olfactory effect of theperfume composition will be the sum of the effects of each of theperfumes or fragrance ingredients. Thus the compounds of the inventioncan be used to alter the aroma characteristics of the perfumecomposition, or by modifying the olfactory reaction contributed byanother ingredient in the composition. The amount will vary depending onmany factors including other ingredients, their relative amounts and theeffect that is desired.

The level of compound of the invention employed in the perfumed articlevaries from about 0.005 to about 10 weight percent, preferably fromabout 0.5 to about 8 and most preferably from about 1 to about 7 weightpercent. In addition to the compounds other agents can be used inconjunction with the fragrance. Well known materials such assurfactants, emulsifiers, polymers to encapsulate the fragrance can alsobe employed without departing from the scope of the present invention.

Another method of reporting the level of the compounds of the inventionin the perfumed composition, i.e., the compounds as a weight percentageof the materials added to impart the desired fragrance. The compounds ofthe invention can range widely from 0.005 to about 70 weight percent ofthe perfumed composition, preferably from about 0.1 to about 50 and mostpreferably from about 0.2 to about 25 weight percent. Those with skillin the art will be able to employ the desired level of the compounds ofthe invention to provide the desired fragrance and intensity.

The following are provided as specific embodiments of the presentinvention. Other modifications of this invention will be readilyapparent to those skilled in the art. Such modifications are understoodto be within the scope of this invention. As used herein all percentagesare weight percent unless otherwise noted, ppm is understood to standfor parts per million and g is understood to be grams. IFF as used inthe examples is understood to mean International Flavors & FragrancesInc., New York, N.Y., USA.

EXAMPLE A Preparation of Cyclopropanepentanol, Alpha, Alpha, Epsilon,Trimethyl-

To a dry 500 ml multi-neck round bottom flask fitted with an airstirrer, nitrogen inlet condenser and an addition funnel 62 g of 99%optically pure DH Myrecerol (IFF)and 1000 ml Methylene Chloride werecharged in a pot and flame dried and cooled to 10° C. The mixture washeated maintained at 60° C. 800 ml of triisobutyl aluminum was chargedin clean dry cannula. The mixture was aged for 7.5 hours. The mixturewas quenched with saturated NH₄Cl, aqueous layer separated and theorganic layer washed with 200 ml of water. The organic layer was thendried over anhydrous MgSO₄ and the final product was recovered with a70% yield.

The odor was described as having a fresh, strong, citrus, lime andherbal fragrance notes.

The NMR of the Cyclopropanepentanol, Alpha, Alpha, Epsilon-Trimethyl- isas follows: 0.1 ppm (m, 1H); 0.3-0.5 ppm (m, 3H); 0.7 ppm (s, 1H); 1.0ppm (d, 3H); 1.2 ppm (s, 7H); 1.3 ppm (m, 1H); 1.4 ppm (m, 5H).

EXAMPLE B Preparation of Cyclopropane1-(1,5-Dimethyl-4-Hexenyl)-1-(Methoxymethyl)-

To a dry 100 ml multi-neck round bottom flask fitted with an airstirrer, nitrogen inlet condenser and an addition funnel 22 g of ether,7.5 g of ZnCu, 26.8 g CH₂I₂ and 31 ml of ether were added and stirred.The mixture was heated maintained at 60° C. The mixture was refluxed at35° C. overnight and the final product was recovered in 70% yield.

The odor was described as having a strong citrus, floral and rosyfragrance notes.

The NMR of the cyclopropane1-(1,5-dimethyl-4-hexenyl)-1-(methoxymethyl)- is as follows: 0.5 ppm (m,4H); 1.0 ppm (s, 4H); 1.3 ppm (s, 1H); 1.5 ppm (d, 3H); 1.7 ppm (s, 3H);1.8 ppm (s, 3H); 2.0 ppm (m, 2H); 3.2 ppm (m, 2H); 3.4 ppm(m, 3H) 5.1ppm (s, 1H).

EXAMPLE C Preparation of Cyclopropanepropanol, Alpha,2-Diethyl-Alpha,2-Dimethyl

To a dry 100 ml multi-neck round bottom flask fitted with an airstirrer, nitrogen inlet condenser and an addition funnel 0.22 mole ofzinc copper, 0.20 mole of methylene iodide, 200 ml of MTBE and 3crystals of I₂ were charged and stirred. 0.10 mole of D.H. Ethyllinanlool was added dropwise and the sample was aged at roomtemperature. Quench with 200 ml of saturated NH4Cl solution, the aqueousphase was separated out and final product was recovered with a 70%yield.

The odor was described as having a refreshingly light, clean, floral,citrus, lemon, orange and sweet fragrance notes.

The NMR of the Cyclopropanepropanol, Alpha, 2-Diethyl-Alpha,2-Dimethylis as follows: 0.4 ppm (m, 1H); 0.5 ppm (m, 1H); 0.9 ppm (m, 2H); 1.0ppm (m, 6H); 1.2 ppm (m, 1H); 1.4 ppm (m, 3H); 1.6 ppm (m, 2H); 1.7 ppm(m, 2H); 1.8 ppm (m, 2H) 2.0 ppm (m, 2H); 2.1 ppm (m, 1H).

EXAMPLE D Demonstration Formula (Shower Gel) with CyclopropanatedDihydro Myrcenol

Aldehyde AA Triplal 15.00 Benzophenone 5.00 Bergamot Oil 100.00 CardamomOil 8.00 Cyclopropanated Dihydro Myrcenol 60.00 Diphenyl Oxide 10.00Galaxolide 100.00 Geranium Oil 12.00 Hedione 60.00 Helional 6.00 Lilial100.00 Lyral 50.00 Melafleur 12.00 Menthol 37.00 Nerol 45.00 PatchouliOil 15.00 Peppermint Oil 40.00 Phenyl Ethyl Alcohol 125.00 Spearmint Oil200.00 Total weight 1000.00

The addition of Cyclopropanated Dihydro Myrcenol to the fragrance in theshower gel formulation lifts the fragrance and enhances the naturalnessof the fragrance.

1. A compound of formula selected from the group consisting of

wherein R and R′ each independently is selected from the groupconsisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, CH(CH₃)CH₂CH₂CH₃,CH₂CH(CH₃)CH₂CH₃, CH₂CH₂CH(CH₃)CH₃, cyclopropyl, cyclobutyl,cyclopentyl, CH═CHCH₂CH₂CH₃, CH₂CH═CHCH₂CH₃, CH₂CH₂CH═CHCH₃, andCH═C(CH₃)CH₂CH₃.
 2. The compound of claim 1, wherein R and R′ eachindependently is a straight, branched or cyclic hydrocarbon moietyconsisting of less then 5 carbon atoms.
 3. A method of improving,enhancing or modifying a fragrance formulation through the addition ofan olfactory acceptable amount of the compound of claim
 1. 4. The methodof claim 3, wherein the fragrance formulation is incorporated into aproduct selected from the group consisting of perfumes, colognes, toiletwaters, cosmetic products, personal care products, fabric care products,cleaning products and air fresheners.
 5. The method of claim 4, whereinthe cleaning products are selected from the group consisting ofdetergents, dishwashing compositions, scrubbing compounds and windowcleaners.
 6. The method of claim 3, wherein the olfactory acceptableamount is from about 0.005 to about 10 weight percent.
 7. The method ofclaim 3, wherein the olfactory acceptable amount is from about 0.5 toabout 8 weight percent.
 8. The method of claim 3, wherein the olfactoryacceptable amount is from about 1 to about 7 weight percent.
 9. Afragrance formulation containing an olfactory effective amount of thecompound of claim
 1. 10. A fragrance product containing the compound ofclaim
 1. 11. A fragrance compound of the structure:


12. A method of improving, enhancing or modifying a fragranceformulation through the addition of an olfactory acceptable amount ofthe compound of claim
 11. 13. The method of claim 12, wherein thefragrance formulation is incorporated into a product selected from thegroup consisting of perfumes, colognes, toilet waters, cosmeticproducts, personal care products, fabric care products, cleaningproducts and air fresheners.
 14. The method of claim 13, wherein thecleaning products are selected from the group consisting of detergents,dishwashing compositions, scrubbing compounds and window cleaners.
 15. Afragrance formulation containing an olfactory effective amount of thecompound of claim 11.